EP2702008B1

EP2702008B1 - Compositions containing polyhydroxyoxoaluminum cations and manufacture thereof

Info

Publication number: EP2702008B1
Application number: EP11810736.6A
Authority: EP
Inventors: John Vaughn; Iraklis Pappas; Long Pan
Original assignee: Colgate Palmolive Co
Current assignee: Colgate Palmolive Co
Priority date: 2011-04-26
Filing date: 2011-12-20
Publication date: 2016-03-09
Anticipated expiration: 2031-12-20
Also published as: US9174851B2; US20140147405A1; CA2834129A1; EP2702008A1; MX361821B; BR112013024919A2; AR086120A1; AU2011366871B2; MX2013012371A; WO2012148481A1; ES2569856T3; RU2013152256A; CO6801753A2; AU2011366871A1; CL2013003093A1

Description

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent Application No. 61/479,081, filed 26 April 2011 .

FIELD OF THE INVENTION

The present invention is directed to compositions containing polyhydroxyoxoaluminum cations and manufacture thereof. These aluminum materials can be used for antiperspirant salts, water treatment, wastewater treatment, dye mordants, taste astringents, and clay pillaring.

BACKGROUND OF THE INVENTION

Aluminum salts, such as aluminum chlorohydrex (also called aluminum chlorohydrex polymeric salts and abbreviated here as "ACH") and aluminum zirconium glycine salts (abbreviated here as "ZAG", "ZAG complexes" or "AZG"), are known to contain a variety of polymeric and oligomeric species with molecular weights (MW) of 100 Da - 500,000 Da.
In an attempt to increase the quality and quantity of smaller aluminum and/or zirconium species, a number of efforts have focused on: (1) how to select the components of ACH and ZAG that affect the performance of these materials; and (2) how to manipulate these components to obtain and/or maintain the presence of smaller types of these components. These attempts have included the development of analytical techniques to identify the components. Size exclusion chromatography ("SEC") or gel permeation chromatography ("GPC") are methods frequently used for obtaining information on polymer distribution in aluminum salt solutions. With appropriate chromatographic columns, generally five distinctive groups of polymer species can be detected in commercial ACH and ZAG complexes appearing in a chromatogram as peaks 1, 2, 3, 4 and a peak known as "5,6", referred to hereinafter as Peak 5. Peak 1 contains the larger Zr species (greater than 60 Angstroms). Peaks 2 and 3 contain larger aluminum species. Peak 4 contains smaller aluminum species (aluminum oligomers, or small aluminum clusters) and has been correlated with enhanced antiperspirant efficacy for both Al and Al/Zr salts. Peak 5 contains the smallest and most acidic aluminum species. Various analytical approaches for characterizing the peaks of ACH and various types of ZAG actives are found in "Antiperspirant Actives--Enhanced Efficacy Aluminum-Zirconium-Glycine (AZG) Salts" by Dr. Allan H. Rosenberg (Cosmetics and Toiletries Worldwide, Fondots, D. C. ed., Hertfordshire, UK: Aston Publishing Group, 1993, pages 252, 254-256).
Attempts to activate antiperspirant salts to produce materials having improved efficacy have included developing processes for obtaining composition having large amounts of Peak 4.
Solutions of partially neutralized aluminum are known to contain a variety of hydrolytic Al species. The identity and distribution of these various forms depends on the hydrolysis ratio (i.e. the OH:Al molar ratio), the Al precursor and the choice of the reaction condition. In the field of antiperspirant (AP) technology, SEC chromatography is the traditional method used for elucidating the distribution of these Al species. Conventional SEC physically separates Al species into domains which are subsequently measured using a concentration detector. It is generally recognized that at least five domains of Al species can be differentiated by size-exclusive chromatography. These domains are commonly referred to Peak 1, Peak 2, Peak 3, Peak 4, and Peak 5, where increasing peak number indicates smaller relative size of the eluting species. Peak 4 and Peak 5 have been implicated as highly efficacious Al domains for antiperspirants. Monomeric Al and low oligomers, are known to elute under Peak 5. Oligomeric polyhydroxyoxoaluminum cations elute under Peak 4.
It is well known in the art that such a variety of hydrolytic Al species exists and that it is possible to distinguish large aqueous aluminum hydroxide molecules using spectroscopic methods such as ²⁷ Al NMR which elucidates the structural environment surrounding Al atoms which are embodied in various forms (Casey WH, "Large Aqueous Aluminum Hydroxide Molecules", Chem. Rev. 2006, 106 (1), pages 1 to 16).
There are two regions in a ²⁷Al NMR spectrum that represent Al nuclei which are octahedrally coordinated (0 ppm - 60 ppm) and tetrahedrally coordinated (60 ppm - 90 ppm). The octahedral region is exemplified by the hexa-aqua Al species, i.e. monomeric Al, which resonates sharply at 0 ppm. The tetrahedral region is exemplified by sharp resonance at 62.5 ppm from the Al₁₃ polyhydroxyoxoaluminum cation. Al₁₃ is composed of 12 octahedrally coordinated Al atoms surrounded by one centrally-cited Al atom which is tetrahedrally coordinated. The Al₃₀ polyhydroxyoxoaluminum cation is essentially a dimer of the Al₁₃ polyhydroxyoxoaluminum cation and contains 2 tetrahedrally coordinated Al atoms which resonate at 70 ppm.
It is known that ²⁷Al NMR spectroscopy may not fully elucidate the chemical composition of a partially neutralized Al salt solution, since there may be a variety of Al species that do not give rise to sharp and unambiguous resonance peaks. These species can be considered as effectively NMR-invisible. Unless the ²⁷Al NMR spectroscopy is carried out quantitatively, the relative concentration of these NMR-invisible species cannot be determined and must be inferred from SEC chromatography.
The state of the art discloses a number of methods for synthesizing and purifying the Al₁₃ polyhydroxyoxoaluminum cation (for example Fu G, et al, "Aging Processes of Alumina Sol-Gels; Characterization of New Aluminum Polycations by 27Al NMR Spectroscopy" Chem. Mater. 1991, 3(4), pages 602 to 610).
It is known that the Al₁₃ polyhydroxyoxoaluminum cation may be converted to obtain the Al₃₀ polyhydroxyoxoaluminum cation by heating a solution of the Al₁₃ polyhydroxyoxoaluminum cation (Roswell J et al, "Speciation and Thermal Transformation in Alumina Sols; Structures of the Polyhydroxyoxoaluminum Cluster [Al30 O8 (OH)56 (H2O)26]18+ and its δ-Keggin Moieté", J. Am. Chem. Soc. 2000, 122, pages 3777 to 3778; Chen Z et al, "Effect of thermal treatment on the formation and transformation of Keggin Al13 and Al30 species in hydrolytic polymeric aluminum solutions", Colloids and Surfaces A: Physiochem. Eng. Aspects, 292 (2007) pages 110 to 118; and Allouche L et al, "Conversion of Al13 Keggin ε into Al30: a reaction controlled by aluminum monomers", Inorganic Chemistry Communications, 6 (2003) pages 1167-1170).
Heating an Al₁₃ solution is the only synthetic pathway to achieving Al₃₀ which has been described in the literature. As well as the references identified above, WO-A-2006/103092 and Shafran KL et al, "The static anion exchange method for generation of high purity aluminum polyoxocations and monodisperse aluminum hydroxide nano-particles", J. Mater. Chem., 2005, 15, pages 3415 to 3423, disclose the use of an ion-exchange process to synthesize Al₁₃ to achieve greater than 90% purity, and disclose heating the thus-formed Al₁₃ solution to form Al₃₀.
Partial neutralization of Al salts have been shown to yield trace quantities of the polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷ Al NMR. There is a need in the art for a high-yield synthetic route to the polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷ Al NMR. The small quantities obtained, lack of purity, and lack of method of making has prevented science from isolating this polycation in sufficient quantity and purity so that its structure could be determined.
It would be desirable to develop a method to make a composition containing a polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷Al NMR in a sufficient quantity so that this cation can be analyzed for chemical structure and physical properties. Such a method could make a composition that has the polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷Al NMR present in a relative abundance that is greater than any other species of aluminum detectable by ²⁷Al NMR.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 is a ²⁷Al NMR spectrograph of material 1 from the examples before heating.
Figure 2 is a ²⁷Al NMR spectrograph of material 1 from the examples after heating.
Figure 3 is a ²⁷Al NMR spectrograph of material 2 from the examples before heating.
Figure 4 is a ²⁷Al NMR spectrograph of material 2 from the examples after heating.

BRIEF SUMMARY OF THE INVENTION

It has been discovered that the Al₃₀ polyhydroxyoxoaluminum cation can be converted to a species of polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷Al NMR. This species also will elute at Peak 4 on a SEC chromatogram. The Al₃₀ polyhydroxyoxoaluminum cation can be obtained from the inventors' earlier work in WO-A-2012/060817 , which was filed on 2 November 2011.
The previous material can be aged for a sufficient time at sufficient temperature to convert the Al₃₀. In one embodiment, the material can be aged at about 100°C for a sufficient period of time, such as about 10 days or greater, or about 30 days or greater. In another embodiment, the material can aged by supercritical heating in an isochoric reaction vessel or under hydrothermal reaction at sufficient temperature and time, such as at 100°C for 5 days. In another embodiment, the material can be aged at ambient conditions (such as 15°C to 60°C) for a period of time of several months, such as at least 6 months, to more than one year.
The present invention accordingly provides composition comprising a polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷Al NMR that is present in a relative abundance on a ²⁷Al NMR spectrograph that is greater than any other polyhydroxyoxoaluminum cation detectable by ²⁷Al NMR.
In some embodiments, the aluminum salt has an OH to Al ratio of at most 2.6:1, and in other embodiments 2:1 to 2.6:1, optionally an OH to Al ratio of 2:1 to 2.5:1, or 2.3:1 to 2.5:1.
The composition may optionally further comprise a buffer, optionally wherein a molar ratio of buffer to aluminum is at least 0.1:1. In other embodiments, the molar ratio is 0.1:1 to 3:1. The buffer may be at least one buffer chosen from an amino acid, betaine, and quat. Optionally, the buffer is an amino acid and a molar ratio of amino acid to aluminum is at least 0.1:1. In some embodiments, the amino acid is glycine.
In some embodiments, the composition has a SEC Peak 4 area of at least 95% of a total area of Peaks 1, 2, 3, 4 and 5 in the SEC chromatogram. In some embodiments, the composition has a SEC Peak 3 area of less than 5% of a total area of Peaks 1, 2, 3, 4 and 5 in the SEC chromatogram, and most preferably has no SEC Peak 3 area in the SEC chromatogram.
In some embodiments, the composition has a SEC Peak 5 area of less than 5% of a total area of Peaks 1, 2, 3, 4 and 5 in the SEC chromatogram, and most preferably has no SEC Peak 5 area in the SEC chromatogram.
In some embodiments, the composition has a SEC Peak 4 area of 95 to 100%, no SEC Peak 3 area, and a SEC Peak 5 area of from 0 to 5% of a total area of Peaks 1, 2, 3, 4 and 5 in the SEC chromatogram.
The composition may further comprise zirconium, and optionally a molar ratio of aluminum to zirconium is 5:1 to 10:1.
A method of making a polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷Al NMR comprising:

heating an aqueous solution containing i) a first aluminum salt containing an Al₃₀ polyhydroxyoxoaluminum cation, ii) an inorganic salt, and iii) a buffer, wherein the buffer is at least one of an amino acid, betaine, and quat, and a molar ratio of buffer to aluminum is at least 0.1:1, wherein the heating is one of
1. a) at a temperature of 100°C to 250°C in an isochoric reactor or under hydrothermal reaction for a time sufficient to form a species of polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷Al NMR; or
2. b) at 100°C at reflux for about 10 days or greater, optionally about 30 days or greater.

The present invention also provides a method of making a polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷ Al NMR comprising storing an aqueous solution containing i) an Al₃₀ polyhydroxyoxoaluminum cation, ii) an inorganic salt, and iii) a buffer, wherein the buffer is at least one of an amino acid, betaine, and quat, and a molar ratio of buffer to aluminum is at least 0.1:1 at a temperature of 15°C to 60°C for a period of time until the polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷Al NMR that is present in a relative abundance on a ²⁷ Al NMR spectrograph that is greater than any other polyhydroxyoxoaluminum cation detectable by ²⁷Al NMR.
In some embodiments, the buffer is glycine. In some embodiments, the inorganic salt is at least one chloride salt chosen from calcium chloride, magnesium chloride, strontium chloride, barium chloride, stannous chloride, and yttrium chloride. In some embodiments, the inorganic base includes at least one member chosen from calcium hydroxide, magnesium hydroxide, strontium hydroxide, barium hydroxide, stannous hydroxide, yttrium hydroxide, calcium oxide, magnesium oxide, strontium oxide, barium oxide, stannous oxide, yttrium oxide, calcium carbonate, magnesium carbonate, strontium carbonate, barium carbonate, stannous carbonate, and yttrium carbonate. Typically, the inorganic base is calcium hydroxide. In some embodiments, the aluminum salt solution has an OH to Al molar ratio of 2.0:1 to 2.5:1 or 2.1:1 to 2.5:1.
In some embodiments, the first aluminum salt is an aluminum chloride compound chosen from aluminum trichloride, aluminum chlorohexahydrate, aluminum dichlorohydrate, and aluminum monochlorohydrate. Optionally, the composition further comprises zirconium. The zirconium compound may be ZrOCl₂·8H₂O or Oxo-Hexameric Zirconium-Octaamino Acid.
The present invention further provides the use of a heating step to convert Al₃₀ polyhydroxyoxoaluminum cations in the species detectable by ²⁷Al NMR within an aqueous aluminum salt solution into a species of polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷ Al NMR, the heating step is one of:

a) at a temperature of 100°C to 250°C in an isochoric reactor or under hydrothermal reaction for a time sufficient to form a species of polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷ Al NMR; or
b) at 100°C at reflux for about 10 days or greater, optionally about 30 days or greater.

In some embodiments, the heating step converts all the Al₁₃ polyhydroxyoxoaluminum cation species present in the aqueous aluminum salt solution into the Al₃₀ polyhydroxyoxoaluminum cation species. In some embodiments, the buffer is glycine.
In some embodiments, the OH:Al molar ratio has been achieved by adding to the aqueous aluminum salt solution an inorganic base including at least one member chosen from calcium hydroxide, magnesium hydroxide, strontium hydroxide, barium hydroxide, stannous hydroxide, yttrium hydroxide, calcium oxide, magnesium oxide, strontium oxide, barium oxide, stannous oxide, yttrium oxide, calcium carbonate, magnesium carbonate, strontium carbonate, barium carbonate, stannous carbonate, and yttrium carbonate. Typically, the inorganic base is calcium hydroxide. Optionally, the OH to Al molar ratio is 2.0:1 to 2.5:1 or 2.1:1 to 2.5:1.
In some embodiments, the aluminum salt is an aluminum chloride compound chosen from aluminum trichloride, acidified aluminum chlorohexahydrate, aluminum dichlorohydrate, and aluminum monochlorohydrate.

DETAILED DESCRIPTION OF THE INVENTION

In this specification, the use of ²⁷Al NMR data is not quantitative but considers only NMR-visible Al species and in particular resonances at 0 ppm, 62.5 ppm, 70 ppm, and 76 ppm. Octahedrally coordinated nuclei are detected via ²⁷Al NMR. The Al monomer resonance at 0 ppm is octahedrally coordinated. Octahedral bands in Al₁₃ and Al₃₀ are broad and overlapping, so they're not useful when identifying Al species. The breadth of octahedral bands in Al₁₃ & Al₃₀ is due to structural and environmental variation. Because the Al nuclei in monomeric Al exist structurally in one form, the signal is narrow, and easily identified. Tetrahedrally coordinated nuclei in Al₁₃ and Al₃₀ also feature minimal variation, which leads to narrow, identifiable NMR signals. ²⁷Al NMR data do not indicate the amount of undetected Al embodied in NMR-invisible species.
When calculating the relative amounts of Al embodied in compositions containing ²⁷Al NMR visible species that have known structures, such as Al₁₃ and Al₃₀ polyhydroxyoxoaluminum cations, the tetrahedral resonance peak of the aluminum is integrated and multiplied by a scaling factor to account for other octahedrally coordinated Al present in the structure. In the Al₁₃ polyhydroxyoxoaluminum cation, there is one tetrahedral resonance peak in the structure. In the Al₃₀ polyhydroxyoxoaluminum cation, there are two tetrahedral resonance peaks in the structure. To convert, the resonance from the Al₁₃ polyhydroxyoxoaluminum cation is multiplied by 13, whereas the resonance from the Al₃₀ polyhydroxyoxoaluminum cation is multiplied by 15. When the structure of the 76 ppm material is identified, a scaling factor can be determined.
For now, the amounts of each species of polyhydroxyoxoaluminum cation in a composition will be characterized by the relative abundance of tetrahedral aluminum resonance peaks on a ²⁷ Al NMR spectrograph. This means that the area of the tetrahedral aluminum resonance peak for a polyhydroxyoxoaluminum cation is compared to the area of the tetrahedral aluminum resonance peaks for other polyhydroxyoxoaluminum cations. The ²⁷ Al NMR spectrograph should be collected at sufficient enough field strength so that all relevant signals can be integrated. One procedure for operating a ²⁷ Al NMR is described in the examples below. In the current state of the art, the resonance frequency is at least 104.2 Mhz to provide a sufficient field strength.
The present invention is directed to a polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷ Al NMR that is present in a relative abundance on a ²⁷ Al NMR spectrograph that is greater than any other polyhydroxyoxoaluminum cation detectable by ²⁷ Al NMR. This means that there are more tetrahedral aluminum atoms resonating at 76 ppm than at any other position in the tetrahedral region of the ²⁷Al NMR spectrograph.
In certain embodiments, the species of polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷ Al NMR is present in a relative abundance on a ²⁷ Al NMR spectrograph that is at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99, 99.5, 99.9, 99.99, or 99.999% of all species of polyhydroxyoxoaluminum cation detectable by ²⁷ Al NMR.
The species of polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷ Al NMR can be made by heating an aqueous solution containing i) an Al₃₀ polyhydroxyoxoaluminum cation, ii) an inorganic salt, and iii) a buffer, wherein the buffer is at least one of an amino acid, betaine, and quat, and a molar ratio of buffer to aluminum is at least 0.1:1, wherein the heating is one of

a) at a temperature of 100°C to 250°C in an isochoric reactor or under hydrothermal reaction for a time sufficient to form a species of polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷ Al NMR;
b) at 100°C at reflux for about 10 days or greater, optionally at least 30 days or greater.

Alternatively, the species of polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷Al NMR can be made by storing an aqueous solution containing i) an Al₃₀ polyhydroxyoxoaluminum cation, ii) an inorganic salt, and iii) a buffer, wherein the buffer is at least one of an amino acid, betaine, and quat, and a molar ratio of buffer to aluminum is at least 0.1:1 at a temperature of 15°C to 60°C for a period of time until the polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷Al NMR that is present in a relative abundance on a ²⁷Al NMR spectrograph that is greater than any other polyhydroxyoxoaluminum cation detectable by ²⁷Al NMR. At these ambient temperatures, the time needed will be several months, such as at least 6 months, to more than one year.
The reaction in the isochoric reactor or under hydrothermal reaction is conducted at 100°C to 250°C. As the temperature increases, the time need to convert Al₃₀ polyhydroxyoxoaluminum cation to the polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷Al NMR decreases. Below are some examples of temperature and time:

i) at 100°C for about 5 days,
ii) at 120°C for about 12 hours, or
iii) at 150°C for about 20 minutes.

The inorganic salt and buffer help to stabilize the species of polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷Al NMR. In certain embodiments, the inorganic salt is at least one chloride salt chosen from calcium chloride, strontium chloride, barium chloride, magnesium chloride, stannous chloride, and yttrium chloride. In one embodiment, the salt is calcium chloride. In certain embodiments, the buffer is glycine. In certain embodiments, the inorganic salt is calcium chloride and the buffer is glycine.
The description below describes methods of obtaining an Al₃₀ polyhydroxyoxoaluminum cation containing composition.
The Al₃₀ containing compositions may be made in a variety of ways involving a stepwise procedure to neutralize aluminum chloride in solution (optionally buffered) using inorganic basic salts. The procedure generally includes the step of heating an aqueous solution containing an aluminum chloride compound (optionally with a buffer agent) at a temperature of 50°C to 100°C, optionally 50°C to 95°C, for a period of time of 1 hour to 6 hours. The heating may be under stirring, such as vigorous stirring, or under reflux. In one such embodiment, an aqueous solution containing an aluminum chloride compound and a buffer agent is heated at a temperature of 75°C to 95°C to reflux for a period of time of 2 hours to 4 hours. In one embodiment, the temperature is 95°C under vigorous stirring for a period of time of 2.5 hours.
To adjust the pH of the aluminum salt solution, an aqueous solution of an inorganic base is added to the heated solution to thereby obtain a pH adjusted aluminum salt solution having a hydroxide to aluminum molar ratio of 1:1 to 4:1, and a pH of 2 to 5. In one such embodiment, the hydroxide to aluminum molar ratio of 2:1 to 3:1. In another such embodiment, the hydroxide to aluminum molar ratio is 2.1:1 to 2.6:1.
In one embodiment, the inorganic base can be at least one base chosen from metal hydroxides, calcium hydroxide, magnesium hydroxide, strontium hydroxide, barium hydroxide, stannous hydroxide, yttrium hydroxide, calcium oxide, magnesium oxide, strontium oxide, barium oxide, stannous oxide, yttrium oxide, calcium carbonate, magnesium carbonate, strontium carbonate, barium carbonate, stannous carbonate, and yttrium carbonate.
Optionally, a buffer can be included. Buffers that can be used can be chosen from amino acids, such as glycine, betaine, such as betaine monohydrate, and quats. The buffer to aluminum molar ratio in certain embodiments can be at least 0.1:1, or 0.1:1 to 3:1. In another embodiment, the buffer to aluminum molar ratio is 0.1: 1 to 2: 1.
In one embodiment, the inorganic base is calcium hydroxide. In one such embodiment, the addition of calcium hydroxide provides an aqueous solution having a Ca(OH)₂:glycine molar ratio of at least 0.1:1.
When a buffer is absent, significant Peak 3 species in the SEC chromatogram begin to form when the total Al concentration is above 0.2M. When a buffer is present, the total Al concentration can reach up to 2.5M while maintaining a predominant Peak 4 in the SEC chromatogram. In one embodiment, an aqueous aluminum chloride salt solution is buffered with glycine and held at 50°C to 95°C under vigorous stirring for a period time of 1 to 6 hours. To the heated solution, an aqueous solution of an inorganic base is added dropwise over a period of time of 1 to 3 hours while maintaining the aluminum-glycine solution at 50°C to 95°C under vigorous stirring. In one such embodiment, the solution has a glycine to aluminum molar ratio of 1.5. In another such embodiment, the solution has a glycine to aluminum molar ratio of 0.5.
In some embodiments, a zirconium salt may also be added to the pH adjusted aluminum salt solution. In one other such embodiment, the molar ratio of Al: Zr is 5:1 to 10:1. The zirconium salt may be simple Zr salts: ZrOCl₂·8H₂O or Oxo-Hexameric Zirconium-Octaamino Acid. In one such embodiment, the molar ratio of Al: Zr is 8. In another such embodiment, the molar ratio of Al: Zr is 7. In one other such embodiment, the molar ratio of Al: Zr is 9.
For the above methods, the aluminum chloride salt and inorganic base may be obtained from a variety of sources. In one embodiment, the aluminum chloride salt includes aluminum trichloride, acidified aluminum chlorohexahydrate, aluminum dichlorohydrate, and aluminum monochlorohydrate. In one such embodiment, the aluminum chloride salt is aluminum chlorohexahydrate.
The present invention provides for aluminum compositions and/or aluminum-zirconium compositions having high levels of low molecular weight Al and Zr species. The high levels of low molecular weight Al and Zr species is reflected in a SEC trace that has an intense Peak 4 and low Peaks 1, 2, 3 and 5. The polymerization of the aluminum species in aqueous solutions and the correspondent gelation process are followed by monitoring the molecular weight profile of the polyoxohalides in time by SEC. The relative retention time ("Kd") for each of these peaks varies depending on the experimental conditions, but the peaks remain relative to each other. The SEC data for the examples is obtained using an SEC chromatogram using the following parameters: Waters®600 analytical pump and controller, Rheodyne® 7725I injector, Protein-Pak® 125 (Waters) column, Waters 2414 Refractive Index Detector. 5.56mM nitric acid mobile phase, 0.50ml/min flow rate, 2.0 microliter injection volume. Data was analyzed using Waters® Empower software (Waters Corporation, Milford, Mass.). The concentration of the aluminum species in aqueous solution does not affect the retention time in the machine.
The levels of the species corresponding to these peaks are estimated based on the following ratios (or percentages): $f_{P_{i}} = \frac{P i}{\sum P j} i = 1, 2, 3, 4, 5; j = 2, 3, 4, 5$

where f_Pi is the fraction of peak i, and Pi or Pj are the intensity of peaks Pi or Pj, respectively. The amount of low molecular weight Al species will be correlated with the fraction, f_P4, or percentage, f_P4 x100, of SEC-Peak 4. In brief, a preferred aluminum species would have a very low f_P1, f_P2, f_P3, and/or f_P5, and a high f_P4.
In certain embodiments, the ratio of Peak 4 to Peak 3 is at least 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, or any number up to infinity. Preferably, Peak 3 is so low as to be undetectable.
In one embodiment, an aluminum salt and/or aluminum-zirconium salt, in aqueous solution, exhibit a SEC profile wherein the SEC Peak 4 to Peak 3 intensity ratio is even as high as infinity, because the Peak 3 is undetectable. In some embodiments, the percentage of SEC Peak 4 of a total area of Peaks 1, 2, 3, 4 and 5 in the SEC chromatogram is: at least at least 90%; at least 95%, or 95 to 100%. In another such embodiment, the SEC Peak 4 area is 100%.
In another embodiment, the aluminum salt and/or the aluminum-zirconium salt, in aqueous solution, exhibits a SEC profile which exhibits low percentage of SEC Peak 3. In such embodiments, the composition has the percentage of SEC Peak 3 area of a total area of Peaks 1, 2, 3, 4 and 5 in the SEC chromatogram is: less than 5 %; less than 2 %; less than 1 %; less than 0.9 %; less than 0.8 %; less than 0.7 %; less than 0.6 %; of less than 0.5 %; less than 0.4 %; less than 0.3 %; less than 0.2 %; or less than 0.1 %. In another such embodiment, the composition has no SEC Peak 3 area.
In another embodiment, the aluminum salt and/or the aluminum-zirconium salt, in aqueous solution, exhibits a SEC profile which exhibits low percentages of SEC Peak 5. In such embodiments, the percentage of SEC Peak 5 area of a total area of Peaks 1, 2, 3, 4 and 5 in the SEC chromatogram is: less than 5 %; or less than 1 %. In another such embodiment, the composition has no SEC Peak 5 area.
In other embodiments, the aluminum salt and/or the aluminum-zirconium salt, in aqueous solution, exhibits a SEC profile which exhibits a low percentage of SEC Peak 1 and a low percentage of SEC Peak 2. In such embodiments, the percentage of SEC Peak 1 area of a total area of Peaks 1, 2, 3, 4 and 5 in the SEC chromatogram is less than 5 %; less than 2 %; or less than 1 %, or the salt has no SEC Peak 1 area. In other embodiments, the percentage of SEC Peak 2 area of a total area of Peaks 1, 2, 3, 4 and 5 in the SEC chromatogram is less than 5 %; less than 2 % or less than 1 %; or the salt has no SEC Peak 2 area. Preferably, the salt has no Peak 1 area and no Peak 2 area. More preferably, the salt has no Peak 1 area, no Peak 2 area and no Peak 3 area. Yet more preferably, the salt has no Peak 1 area, no Peak 2 area, no Peak 3 area and no Peak 5 area.
The compositions of this invention may be used to formulate many different aluminum containing materials. Examples include, but are not limited to, antiperspirant salts, water treatment, wastewater treatment, and clay pillaring.
The present invention is exemplified by the following non-limiting Examples.

EXAMPLES

Two materials prepared in accordance with WO-A-2013/060817 are provided. The materials are aqueous systems that contain the glycine buffer and the calcium chloride byproduct of the manufacturing process.
The raw integration values for ²⁷Al NMR spectroscopy peaks for these materials are listed below in Table 1, and Table 2 shows the relative abundance. The materials are analyzed by taking a 1 M solution and diluting in a 1:4 ratio using D₂O. The final Al concentration for all samples is 0.25M. The samples are analyzed at a ²⁷Al resonance frequency of 104.2 MHz at 90°C. A coaxial insert containing NaAlO₂ is included to provide a reference resonance peak at 80ppm. The instrument collects 1500 transients, with a pulse width of 6.4µs and a delay time of 2 seconds. The data for the relevant peaks are shown in the tables below. The full spectrographs can be seen in Figures 1 to 4.
Material 1 is held at reflux for 30 days at 100°C. Material 2 is subjected to 100°C for 5 days in an isochoric reaction vessel. For comparative purposes, the following discussion relates only with the relative integrations instead of raw data.
For Material 1, the Al₃₀ signal (encompassing 96.10% of the total visible tetrahedral Al) is converted to a signal at 76 ppm (97.76% Td Al). Also, the amount of Al₁₃ is reduced from 3.90% to 2.24%.

For Material 2, the Al₃₀ signal at 70 ppm (encompassing 98.44% of the total visible tetrahedral Al) is converted to a signal at 76 ppm (99.37% Td Al). Also, the amount of Al₁₃ is reduced from 1.56% to 0.63%.

TABLE 1

Material	76 ppm	70 ppm	63 ppm	Total Visible T_d Al
Material 1 untreated	None detected	906.11	36.75	942.86
Material 1 treated	1054.37	None detected	24.15	1078.52
Material 2 untreated	None detected	1585.97	25.09	1611.06
Material 2 Treated	1453.69	None detected	9.20	1462.89

Table 2

Material	Relative Abundance %
Material	76 ppm	70ppm	63 ppm
Material 1 untreated	0	96.10	3.90
Material 1 treated	97.76	0	2.24
Material 2 untreated	0	98.44	1.56
Material 2 Treated	99.37	0	0.63

As used throughout, ranges are used as shorthand for describing each and every value that is within the range. Any value within the range can be selected as the terminus of the range. In the event of a conflict in a definition in the present disclosure and that of a cited reference, the present disclosure controls.
Unless otherwise specified, all percentages and amounts expressed herein and elsewhere in the specification should be understood to refer to percentages by weight. The amounts given are based on the active weight of the material.

Claims

A composition comprising a polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷Al NMR that is present in a relative abundance on a ²⁷Al NMR spectrograph that is greater than any other polyhydroxyoxoaluminum cation detectable by ²⁷Al NMR.
The composition of claim 1, wherein the species of polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷Al NMR is present in a relative abundance on a ²⁷ Al NMR spectrograph that is at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99, 99.5, 99.9, 99.99, or 99.999% of all species of polyhydroxyoxoaluminum cation detectable by ²⁷Al NMR.
The composition of any foregoing claim, further comprising a buffer, wherein a molar ratio of buffer to aluminum is at least 0.1:1, or optionally 0.1:1 to 3:1;
optionally wherein the buffer is at least one buffer chosen from an amino acid, betaine, and quat;
further optionally wherein the buffer is an amino acid and a molar ratio of amino acid to aluminum is at least 0.1, optionally the amino acid is glycine.
The composition of any foregoing claim, wherein the composition further comprises zirconium;
optionally wherein a molar ratio of aluminum to zirconium is 5:1 to 10:1.
A method of making a polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷Al NMR comprising:
heating an aqueous solution containing i) a first aluminum salt containing an Al₃₀ polyhydroxyoxoaluminum cation, ii) an inorganic salt, and iii) a buffer, wherein the buffer is at least one of an amino acid, betaine, and quat, and a molar ratio of buffer to aluminum is at least 0.1:1, wherein the heating is one of
a) at a temperature of 100°C to 250°C in an isochoric reactor or under hydrothermal reaction for a time sufficient to form a species of polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷Al NMR; or

b) at 100°C at reflux for about 10 days or greater, optionally about 30 days or greater.
A method of making a polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷Al NMR comprising storing an aqueous solution containing i) an Al₃₀ polyhydroxyoxoaluminum cation, ii) an inorganic salt, and iii) a buffer, wherein the buffer is at least one of an amino acid, betaine, and quat, and a molar ratio of buffer to aluminum is at least 0.1:1 at a temperature of 15°C to 60°C for a period of time until the polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷Al NMR that is present in a relative abundance on a ²⁷Al NMR spectrograph that is greater than any other polyhydroxyoxoaluminum cation detectable by ²⁷Al NMR.
The method of claim 6, wherein the storing is for at least 6 months, optionally at least one year.
The method of claim 5 or 6, wherein the inorganic salt is at least one chloride salt chosen from calcium chloride, strontium chloride, barium chloride, magnesium chloride, stannous chloride, and yttrium chloride.
The method of claim 5 or 6, wherein the buffer is glycine;
or wherein the inorganic salt is calcium chloride and the buffer is glycine.
The method of claim 5, wherein heating in the isochoric reactor or under hydrothermal reaction is one of
i) at 100°C for about 5 days,

ii) at 120°C for about 12 hours, or

iii) at 150°C for about 20 minutes.
The method of any one of claims 5 to 10, wherein the composition further comprises zirconium;
optionally wherein the zirconium compound is simple Zr salts, ZrOCl₂·8H₂O or Oxo-Hexameric Zirconium-Octaamino Acid.
Use of a heating step to convert Al₃₀ polyhydroxyoxoaluminum cations in the species detectable by ²⁷Al NMR within an aqueous aluminum salt solution into a species of polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷Al NMR, the heating step is one of:
a) at a temperature of 100°C to 250°C in an isochoric reactor or under hydrothermal reaction for a time sufficient to form a species of polyhydroxyoxoaluminum cation detectable at 76 ppm by ²⁷Al NMR; or

b) at 100°C at reflux for about 10 days or greater, optionally about 30 days or greater.
The use according to claim 12, wherein the aqueous aluminum salt solution i) has an aluminum to chloride molar ratio of 0.3:1 to 3:1; ii) contains an inorganic salt, and iii) contains a buffer, wherein the buffer is at least one of an amino acid, betaine, and quat, and a molar ratio of buffer to aluminum is at least 0.1:1; an OH:Al molar ratio of at most 2.6:1, or optionally, 2:1 to 2.6:1;
optionally wherein the buffer is glycine.
The use according to any one of claims 12 to 13, wherein the OH:Al molar ratio has been achieved by adding to the aqueous aluminum salt solution an inorganic base including at least one member chosen from calcium hydroxide, magnesium hydroxide, strontium hydroxide, barium hydroxide, stannous hydroxide, yttrium hydroxide, calcium oxide, magnesium oxide, strontium oxide, barium oxide, stannous oxide, yttrium oxide, calcium carbonate, magnesium carbonate, strontium carbonate, barium carbonate, stannous carbonate, and yttrium carbonate;
optionally wherein the inorganic base is calcium hydroxide.
The use of any one of claims 12 to 14, wherein the OH to Al molar ratio is 2:1 to 2.5:1, or optionally 2.3:1 to 2.5:1.
The use of any one of claims 12 to 15, wherein the aluminum salt is an aluminum chloride compound chosen from aluminum trichloride, aluminum chlorohexahydrate, aluminum dichlorohydrate, and aluminum monochlorohydrate.